Achiral Ligands Research Articles

Recent Advances in Radical Reactions of 1,n‐Enynes with Phosphorus‐Centered Radicals

AbstractOrganophosphorus compounds have been widely used as achiral and chiral ligands in organic synthesis (PPh3, BINAP, dppe, Duphos, Xantphos, PPFA, Chiraphos, SEGPHOS), flame retardants, functional materials (LED, PV), as well as agrochemicals and medicines due to their broad biological activities. As the privileged versatile building blocks, 1,n‐enynes have been successfully applied in the synthesis of various functionalized cyclic compounds based on their two active unsaturated chemical bonds (C═C double and C≡C triple bonds). With the development of highly selective and efficient methods in organic chemistry, various organophosphorus cyclic compounds synthesis through radical cascade strategy has attracted considerable attention in recent years. In here, we have summarized the recent main achievements in the radical cascade reactions of 1,n‐enynes with phosphorus‐centered radicals. Furthermore, we also displayed the detailed reaction mechanisms in this review.

Achiral and chiral ligands synergistically harness chiral self-assembly of inorganics.

Chiral structures and functions are essential natural components in biominerals and biological crystals. Chiral molecules direct inorganics through chiral growth of facets or screw dislocation of crystal clusters. As chirality promoters, they initiate an asymmetric hierarchical self-assembly in a quasi-thermodynamic steady state. However, achieving chiral assembly requires a delicate balance between intricate interactions. This complexity causes the roles of achiral-chiral and inorganic components in crystallization to remain ambiguous. Here, we elucidate a definitive mechanism using an achiral-chiral ligand strategy to assemble inorganics into hierarchical, self-organized superstructures. Achiral ligands cluster inorganic building blocks, while chiral ligands impart chiral rotation. Achiral and chiral ligands can flexibly modulate the chirality of superstructures by fully using their competition in coordination chemistry. This dual-ligand strategy offers a versatile framework for engineering chiroptical nanomaterials tailored to optical devices and metamaterials with optical activities across a broad wavelength range, with applications in imaging, detection, catalysis, and sensing.

N-Heterocyclic Carbene Enabled Copper Catalyzed Asymmetric Synthesis of Pyrimidinyl Phosphine with both Axial and P-Stereogenicity.

P-stereogenic phosphines, renowned for their utility as ligands and catalysts, have been instrumental in the field of asymmetric catalysis. However, the catalytic asymmetric synthesis of chiral ligands possessing both axial and phosphine chirality remains a significant challenge. Here, we present the successful demonstration of a Cu-catalyzed asymmetric C-P construction using in situ generated secondary phosphine and heteroaryl chloride. By introducing a chiral NHC ligand and an achiral diphosphine auxiliary ligand, we effectively alleviated the poisoning effect caused by phosphine(III) compounds and suppressed the nonenantioselective background reaction. The reaction exhibited excellent enantioselectivity, with up to 96 % ee, and good diastereoselectivity, with up to 14 : 1 dr, when employing less sterically hindered secondary phosphines. This particular substrate poses a significant challenge due to its strong poisoning effect in copper catalysis.

Asymmetric dihydroboration of allenes enabled by ligand relay catalysis

Catalytic asymmetric hydroboration of unsaturated bonds has been recognized as the most straightforward method for the construction of chiral organoboron compounds. Although catalytic asymmetric hydroboration of alkenes has been well-developed, enantioselective hydroboration of allenes still remains rare probably due to the challenges in controlling the enantio-, stereo-, and regioselectivity. Additionally, the hydroboration products might go through over-borohydride, making the catalytic asymmetric dihydroboration of allenes challenging. Here, we report a cobalt-catalyzed asymmetric dihydroboration of allenes using a ligand relay strategy with two simple ligands. This protocol shows excellent enantio-, stereo-, and regioselectivity with positive functional group compatibilities in the construction of chiral 1,4-diboronate products. The applications of this reaction are demonstrated by various product derivatizations, gram-scale reactions, and the preparation of artigenin analogues. Mechanistic studies indicate that the achiral ligand controls the first hydroboration of allenes, and the chiral oxazoline iminopyridine ligand is responsible for the subsequent isomerization and asymmetric hydroboration.

Enhanced Enantioselective Discrimination Regulated by Achiral Ligands in Chiral Metal-Organic Frameworks.

Enantioselective recognition is a fundamental property of chiral linkers in chiral metal-organic frameworks (CMOFs). However, clarifying the efficient enantioselective discrimination tailored by achiral linkers remains challenging to explain the chiral recognition mechanism and efficiency. Here, two CMOFs ([Zn2(l-Phe)2(bpa)2]n and [Zn2(l-Phe)2(bpe)2]n) with the completely different enantioselective recognition are synthesized from different nonchiral ligands and the same chiral ligands. The enantioselective recognition of CMOF is undoubtedly related to l-Phe, which differs in the hydrogen bonding to the Trp enantiomer. However, the electrochemical signals are weak and undifferentiated. [Zn2(l-Phe)2(bpe)2]n produces a flattened coplanar conformation with the -C═C- tether in the achiral ligand. The flattened achiral bpee ligand and its surrounding chiral phenylalanine molecules interact through multiple π-π stacking and hydrogen bonding, which together create a chiral sensor that facilitates the recognition of l-Trp. However, [Zn2(l-Phe)2(bpa)2]n produces a stepped conformation due to the -C-C- tether in the achiral ligand; despite the recognition effect of bpea, the recognition is unsatisfactory. Therefore, the chiral recognition of the two CMOFs stems from the synergistic effect between chiral and achiral ligands. This work shows that nonchiral ligands are also crucial in determining enantiomeric discrimination and opens up a new avenue for designing chiral materials.

On the gold(I)-catalyzed enantioselective addition of indole to diphenylallene via anion-binding catalysis

Neutral dual hydrogen bond donors (HBDs) are effective catalysts that enhance the electrophilicity of substrates or the Lewis/Brønsted acidity of reagents through an anion-binding mechanism. Despite their success in various enantioselective organocatalytic reactions, their application to transition metal catalysis remains rare. Herein, we report the activation of gold(I) precatalysts by chiral ureas, leading to enantioselective hydroarylation of allenes with indoles. Experimental and computational studies support an anion-binding mechanism for gold(I) precatalyst activation. Noncovalent interactions were identified as the source of enantiodifferentiation, providing insights into the cooperativity between achiral phosphine ligands and chiral ureas.

Spontaneous resolution and magnetic properties of lanthanide metal organic frameworks based on oxydiacetate

Chiral lanthanide metal organic frameworks (Ln-MOFs) have become a kind of promising platform for developing various chiral functional materials. However, their members are still scarce up to now, especially those obtained from spontaneous resolution. In this work, two pairs of enantiomers of chiral Ln-MOFs, namely, [Ln2(oda)3(H2O)4]·2H2O [Ln = Dy (Λ-1 and Δ-1), Gd (Λ-2 and Δ-2); oda = oxydiacetate], have been prepared from an achiral H2oda ligand by spontaneous resolution. They display homochiral Λ- or Δ-configurational 2D grid-like frameworks in the absence of any chiral source, where four carboxylate groups of oda2− ligands within each [LnIII(oda)3]3− module link to adjacent four Ln ions either in a left- or right-handed fashions. Their homochirality was further confirmed by solid-state circular dichroism (CD) spectrum. Magnetic measurements revealed that Λ-1 exhibits field-induced dual-relaxation behavior of single-molecule magnet (SMM). The effective energy barrier (Ueff) and relaxation time (τ0) of slow relaxation (SR) process are 92.63 K and 1.49 × 10−12 s, respectively. Furthermore, Λ-2 was found to show magnetocaloric effect (MCE), with the maximum magnetic entropy change (−ΔSm) of 10.02 J kg−1 K−1 at 7.0 T and 2.0 K.

Carborane-Cluster-Wrapped Copper Cluster with Cyclodextrin-like Cavities for Chiral Recognition.

Chiral atomically precise metal clusters, known for their remarkable chiroptical properties, hold great potential for applications in chirality recognition. However, advancements in this field have been constrained by the limited exploration of host-guest chemistry, involving metal clusters. This study reports the synthesis of a chiral Cu16(C2B10H10S2)8 (denoted as Cu16@CB8, where C2B10H12S2H2 = 9,12-(HS)2-1,2-closo-carborane) cluster by an achiral carboranylthiolate ligand. The chiral R-/S-Cu16@CB8 cluster features chiral cavities reminiscent of cyclodextrins, which are surrounded by carborane clusters, yet they crystallize in a racemate. These cyclodextrin-like cavities demonstrated the specific recognition of amino acids, as indicated by the responsive output of circular dichroism and circularly polarized luminescence signals of Cu16 moieties of the Cu16@CB8 cluster. Notably, a quantitative chiroptical analysis of amino acids in a short time and a concomitant deracemization of Cu16@CB8 were achieved. Density functional tight-binding molecular dynamics simulation and noncovalent interaction analysis further unraveled the great importance of the cavities and binding sites for chiral recognition. Dipeptide, tripeptide, and polypeptide containing the corresponding amino acids (Cys, Arg, or His residues) display the same chiral recognition, showing the generality of this approach. The functional synergy of dual clusters, comprising carborane and metal clusters, is for the first time demonstrated in the Cu16@CB8 cluster, resulting in the valuable quantification of the enantiomeric excess (ee) value of amino acids. This work opens a new avenue for chirality sensors based on chiral metal clusters with unique chiroptical properties and inspires the development of carborane clusters in host-guest chemistry.

Switchable supramolecular helices for asymmetric stereodivergent catalysis

Despite recent developments on the design of dynamic catalysts, none of them have been exploited for the in-situ control of multiple stereogenic centers in a single molecular scaffold. We report herein that it is possible to obtain in majority any amongst the four possible stereoisomers of an amino alcohol by means of a switchable asymmetric catalyst built on supramolecular helices. Hydrogen-bonded assemblies between a benzene-1,3,5-tricarboxamide (BTA) achiral phosphine ligand coordinated to copper and a chiral BTA comonomer are engaged in a copper-hydride catalyzed hydrosilylation and hydroamination cascade process. The nature of the product stereoisomer is related to the handedness of the helices and can thus be directed in a predictable way by changing the nature of the major enantiomer of the BTA comonomer present in the assemblies. The strategy allows all stereoisomers to be obtained one-pot with similar selectivities by conducting the cascade reaction in a concomitant manner, i.e. without inverting the handedness of the helices, or sequentially, i.e. by switching the handedness of the supramolecular helices between the hydrosilylation and hydroamination steps. Supramolecular helical catalysts appear as a unique and versatile platform to control the configuration of molecules or polymers embedding several stereogenic centers.

Crystallization-Induced Chirality Transfer in Conformationally Flexible Azahelicene Au(I) Complexes with Circularly Polarized Luminescence Activation.

Flexible and twisted annulated π-systems exhibit numerous unique and desirable features, owing to their ability to display chirality. However, preventing their racemization due to the dynamic nature of their chirality remains a challenge. One promising approach to stabilize homochirality in such systems is chirality transfer from a chiral auxiliary to a moiety displaying dynamic chirality. Herein, we introduce a new approach for dynamic chirality stabilization in conformationally flexible azahelicene species via crystallization-induced intermolecular chirality transfer in Au(I) complexes featuring azahelicene (dibenzo[c,g]carbazole and benzo[c]carbazole) and enantio-pure chiral N-heterocyclic carbene (NHC) ligands with a complementary tailored shape. Crystallization of these azahelicene Au(I) complexes not only suppresses the dynamic chirality of the dibenzocarbazole species but also stabilizes their homochirality through the intermolecular conjunction between the chiral NHC and dibenzocarbazole ligands. In the Au(I) benzocarbazole complexes, the intermolecular conjunction and chirality transfer in the crystals induce chirality in the initially achiral benzocarbazole ligand. Furthermore, the crystallization of the studied complexes activates their circularly polarized luminescence (CPL) properties, which were suppressed in solution. Importantly, chirality transfer leads to significant CPL enhancement; the complexes that feature chirality transfer within the crystal structure exhibit luminescence dissymmetry factors 5 to 10 times higher than those of the complexes without chirality transfer.

Induced Absolute Configuration of Achiral Tetradentate Ligands in Metal–Organic Frameworks for Circularly Polarized Luminescence

Comprehensive SummaryThe crystallization of chiral molecules is of great significance to understand the origin and evolution of hierarchical chirality and reveal the relationships between structural chirality and circularly polarized luminescence (CPL) activity. Here, we report two pairs of chiral metal–organic frameworks (MOFs) (DCF‐17/LCF‐17, DCF‐18/LCF‐18) by utilizing tetradentate ligands tetra(3‐imidazoylphenyl)ethylene (TIPE) and 4,4'‐[4',5'‐bis[4‐(4‐pyridinyl)phenyl][1,1':2',1”‐terphenyl]‐4,4”‐diyl]bis[pyridine] (TPPP) as linkers. It can be observed that the spontaneous resolution of the achiral ligands is converted into the induced resolution, and the ligands form the absolute configuration by using enantiopure camphoric acid (cam) as chiral induced reagent (CIR). As a result, the racemate MOFs can be driven to generate absolute homochiral crystallization. Another two achiral MOFs [Cd(D‐cam)(TPPP)0.5] (AF‐1, AF = achiral framework) and [Cd(L‐cam)(TPPP)0.5] (AF‐2) were prepared. The position disorder of D/L‐cam skeleton causes the generation of nonchiralization, further leading to disappearance of symmetry breaking of TPPP. For the perspective of structure, this is the first report which reveals the chiral transfer and nonchiralization between chiral induced agents and tetradentate ligands. Besides, DCF‐17 and LCF‐17 show CPL with luminescence dissymmetry factor (glum) of –1.0 × 10‐2 and +9.2 × 10–3, respectively. This work provides the useful evidences to reveal the induced chiral crystallization and the construction of CPL‐active crystalline materials.

Guest‐Facilitated Heteroleptic Assembly of Helical Anionocages Enables Reversible Chirality Modulation

AbstractWe report a novel strategy for reversible modulation of the supramolecular chirality based on guest‐facilitated heteroleptic assembly of helical anionocages. Two triple‐stranded helical anionocages including a chiral cage 1 (A2L13) and a crown ether functionalized achiral cage 2 (A2L23) were synthesized by anion coordination of bis‐monourea‐based ligands and PhPO32−. Both cages exhibited favorable binding with tetraethylammonium TEA+ and cobaltocenium Cob+ (endo‐guest, bound in the cavity). Additionally, cage 2 could reversibly release and recapture the guests through binding the exo‐guest potassium ions (K+) in the crown ethers and subsequent removal of the K+ by [2,2,2]‐cryptand. The circular dichroism (CD) spectrum of cage 1 was not significantly affected by guest encapsulation or mixing with the “empty” cage 2. However, in the presence of both cage 2 and an endo‐guest/exo‐guest, the Cotton effects were reversed at 391 nm and significantly enhanced at 310 nm. This observation was attributed to the guest‐facilitated formation of heteroleptic cages that enabled effective chirality transfer from the chiral to the achiral ligands. The CD changes induced by K+ could be fully reversed by removing it with [2,2,2]‐cryptand. Sequential addition and removal of K+ allowed reversible modulation of the chirality for at least 10 cycles without significant attenuation.

Guest-Facilitated Heteroleptic Assembly of Helical Anionocages Enables Reversible Chirality Modulation.

We report a novel strategy for reversible modulation of the supramolecular chirality based on guest-facilitated heteroleptic assembly of helical anionocages. Two triple-stranded helical anionocages including a chiral cage 1 (A2 L1 3 ) and a crown ether functionalized achiral cage 2 (A2 L2 3 ) were synthesized by anion coordination of bis-monourea-based ligands and PhPO3 2- . Both cages exhibited favorable binding with tetraethylammonium TEA+ and cobaltocenium Cob+ (endo-guest, bound in the cavity). Additionally, cage 2 could reversibly release and recapture the guests through binding the exo-guest potassium ions (K+ ) in the crown ethers and subsequent removal of the K+ by [2,2,2]-cryptand. The circular dichroism (CD) spectrum of cage 1 was not significantly affected by guest encapsulation or mixing with the "empty" cage 2. However, in the presence of both cage 2 and an endo-guest/exo-guest, the Cotton effects were reversed at 391 nm and significantly enhanced at 310 nm. This observation was attributed to the guest-facilitated formation of heteroleptic cages that enabled effective chirality transfer from the chiral to the achiral ligands. The CD changes induced by K+ could be fully reversed by removing it with [2,2,2]-cryptand. Sequential addition and removal of K+ allowed reversible modulation of the chirality for at least 10 cycles without significant attenuation.

"Sergeants-and-soldiers" principle in the synthesis of intrinsically chiral Au13 clusters.

Surface ligand modification on atomically precise metal clusters is one of the important strategies not only to stabilize monodisperse clusters, but also to derive unique optical and electronic properties. The chiral coordination of surface ligands on clusters controls the global chirality in clusters giving rise to unambiguous optical activity including circular dichroism (CD) and circularly polarized luminescence (CPL). Stereoselective synthesis of intrinsically chiral clusters has been achieved by the use of chiral ligands stabilizing one-handed clusters selectively. Herein, we investigate the effect of chiral ligand coordination on the deracemization of intrinsically chiral Au13 superatom clusters. The mixture of achiral bis(diphenylphosphino)ethane (DPPE) and chiral (R,R)-1,2-bis[(2-methoxyphenyl)phenylphosphino]ethane (R-DIPAMP) led to the formation of a mixture of [Au13(R-DIPAMP)x(DPPE)5-xCl2]3+ clusters with varied x-values (x = 0-5). Reverse phase HPLC successfully fractionalized the mixture into solutions composed of single component Au13 clusters depending on the x-values. The separated Au13 clusters afforded similar optical activity to that of [Au13(R-DIPAMP)5Cl2]3+ in the CD study regardless of x-values (x = 1-4). The DFT calculation supports that the coordination of a single DIPAM ligand is enough to bias the twisting direction in the Au13 superatom with dictating the tortional orientation of other four DPPE ligands. The emergence of the "sergeants-and-soldiers principle", wherein a small number of chiral ligands determine the chiral orientation of other achiral ligands, is thus demonstrated in the synthesis of intrinsically chiral Au13 clusters.

Boosting circularly polarized luminescence by optimizing off-centering octahedral distortion in zero-dimensional hybrid indium-antimony halides.

Chiral zero-dimensional hybrid metal halides (0D HMHs) are being extensively studied as they can directly generate circularly polarized luminescence (CPL) with high photoluminescence quantum yields (PLQYs), yet improving their luminescence dissymmetry factor (g lum) remains a challenge. This study proposes a general strategy to boost the g lum value of chiral 0D HMHs by optimizing the off-centering distortion of inorganic octahedra. Accordingly, (R/S-MBA)2(2MA)In0.95Sb0.05Cl6 (MBA = α-methylbenzylammonium, 2MA = dimethylamine) and (R/S-MBA)2(3MA)In0.95Sb0.05Cl6 (3MA = trimethylamine) with near-unity PLQYs are accordingly synthesized. With increasing the from 0.012 to 0.020, the |g lum| is accordingly increased from 7.8 × 10-3 to 2.0 × 10-2. Notably, the |g lum| can be further boosted to an impressive value of 3.8 × 10-2 while maintaining near-unity PLQYs by continuously increasing the . Experimental results reveal that the choice of achiral ligands and varied Sb3+ dopant concentrations can modulate the distribution and strength of hydrogen bonds around indium-antimony halogen octahedra, respectively, thus regulating the parameter of octahedra in 0D hybrid metal halides. Additionally, light-emitting diodes with a polarization of 1.6% are fabricated. This work sheds light on the relationship between the distortion of inorganic octahedra and the g lum value.

DFT Study on the Mechanism of the Palladium-Catalyzed [3 + 2] Annulation of Aromatic Amides with Maleimides via Benzylic and meta-C-H Bond Activation: Role of the External Ligand Ac-Gly-OH.

The mechanism of the Ac-Gly-OH-assisted palladium-catalyzed [3 + 2] annulation of aromatic amides with maleimides is investigated using density functional theory calculations. The results show that the reaction undergoes the sequential steps of N-H bond deprotonation, first benzylic C-H bond activation, maleimide insertion, second meta-C-H bond activation, reductive elimination, and oxidation. The external ligand Ac-Gly-OH acts as the internal base for hydrogen abstraction in the first benzylic C-H bond activation. The maleimide insertion step is found to be the rate-determining step. Based on the nearly same energetic span of the two pathways to generate the enantio products, the computational results are consistent with the experimental observation that the terminal [3 + 2] annulation products are racemic when using an achiral ligand. These calculation results disclose the detailed reaction mechanism and shed light on some experimental ambiguities.

Novel Chiral CsPbBr3 Metal Halide Perovskite Magic-Sized Clusters and Metal Halide Molecular Clusters with Achiral Ligands.

We have synthesized inherently chiral cesium lead halide perovskite magic-sized clusters (PMSCs) and ligand-assisted metal halide molecular clusters (MHMCs) using the achiral ligands octanoic acid (OCA) and octylamine (OCAm). UV-vis electronic absorption was used to confirm characteristic absorption bands while circular dichroism (CD) spectroscopy was utilized to determine their chiroptical activity in the 412-419 and 395-405 nm regions, respectively. In contrast, the larger sized counterpart of PMSCs, namely, perovskite quantum dots (PQDs), do not show chirality. The inherent chirality of the clusters is tentatively attributed to a twisted chiral layered structure, defect-induced chiral structure, or twisted Pb-Br octahedra.

Factors Controlling Complex Morphologies of Isomorphous Metal-Organic Frameworks.

We demonstrate here how nitrate salts of bivalent copper, nickel, cobalt, and manganese, along with an achiral organic ligand, assemble into various structures such as symmetrical double-decker flowers, smooth elongated hexagonal bipyramids, and hexagonal prisms. Large morphological changes occur in these structures because of different metal cations, although they maintain isomorphous hexagonal crystallographic structures. Metal cations with stronger coordination to ligands (Cu and Ni) tend to form uniform crystals with unusual shapes, whereas weaker coordinating metal cations (Mn and Co) produce crystals with more regular hexagonal morphologies. The unusual flower-like crystals formed with copper nitrate have two pairs of six symmetrical petals with hexagonal convex centers. The texture of the petals indicates dendritic growth. Two different types of morphologies were formed by using different copper nitrate-to-ligand ratios. An excess of the metal salt results in uniform and hexagonal crystals having a narrow size distribution, whereas the use of an excess of ligand results in double-decker morphologies. Mechanistically, an intermediate structure was observed with slightly concave facets and a domed center. Such structures most likely play a key role in the formation of double-decker crystals that can be formed by fusion processes. The coordination chemistry results in isostructural chiral frameworks consisting of two types of continuous helical channels. Four pyridine units from four separate ligands are coordinated to the metal center in a plane having a chiral (propeller-type) arrangement. The individual double-decker flower crystals are homochiral and a batch consists of crystals having both handedness.

Spontaneous Resolution of Chiral Janus-Type Double-Layered Metallocyclic Strips Incorporating Möbius Ring and Circular Helicate.

Homochiral metal-organic macrocyclic complexes are of great significance owing to their chirality and well-defined internal cavities that potentially have the ability to mimic complicated biological processes. Here we report a novel metal/anion-coordination co-driven strategy for the formation of nanoscale supramolecular metallocycles with unique topology, large size, and desired chirality. The enantiomeric Janus-type metallocyclic strips are assembled based on the synergistic coordination of sulfate anions and CoII ions to a bifunctional achiral ligand combining the o-phenylene-(bis)urea anion-chelating and 8-hydroxyquinoline metal-coordinating sites. The inherent chirality arises from two types of helical chiralities (triply twisted Möbius ring and circular helicate), which is observed for the first time for metal-organic complex systems. Notably, spontaneous chiral resolution by conglomerate crystallization into a pair of enantiomers (P- or M-Co9) is realized, which is attributed to the multiple weak intermolecular interactions facilitating the hierarchically helical superstructure.

Integrating Achiral and Chiral Organic Ligands in Zero-Dimensional Hybrid Metal Halides to Boost Circularly Polarized Luminescence.

Chiral zero-dimensional hybrid metal halides (0D HMHs) could combine excellent optical properties and chirality, making them promising for circularly polarized luminescence (CPL). However, chiral 0D HMHs with efficient CPL have been rarely reported. Here, we propose an efficient strategy to achieve simultaneously high photoluminescence quantum yield (PLQY) and large dissymmetry factor (glum ), by integrating achiral and chiral ligands into 0D HMHs. Specifically, three pairs of chiral 0D hybrid indium-antimony chlorides are synthesized by combing achiral guanidine with three types of chiral methylbenzylammonium-based derivatives as the organic cations. These chiral 0D HMHs exhibit near-unity PLQY and large glum values up to around ±1×10-2 . The achiral guanidine ligand is not only essential to crystallize these hybrid indium-antimony chlorides to achieve near-unity PLQYs, but also greatly enhances the chirality induction from organic ligands to inorganic units in these 0D HMHs. Furthermore, the choice of different chiral ligands can modify the strength of hydrogen bonding interactions in these 0D HMHs, to maximize their glum values. Overall, this study provides a robust way to realize efficient CPL in chiral HMHs, expanding their applications in chiroptical fields.